CN105385313B - The manufacture method of anti-charged membrane - Google Patents
The manufacture method of anti-charged membrane Download PDFInfo
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- CN105385313B CN105385313B CN201510520490.2A CN201510520490A CN105385313B CN 105385313 B CN105385313 B CN 105385313B CN 201510520490 A CN201510520490 A CN 201510520490A CN 105385313 B CN105385313 B CN 105385313B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/16—Anti-static materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
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- C08J7/056—Forming hydrophilic coatings
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
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- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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Abstract
The manufacture method of the anti-charged membrane of the present invention, has：Modulating process, the mixing pva into electroconductive polymer aqueous dispersions, so as to modulate mixed liquor, above-mentioned electroconductive polymer aqueous dispersions are the electroconductive polymer aqueous dispersions that the conductive composite body containing pi-conjugated system's electroconductive polymer and polyanion is contained in water system decentralized medium；Working procedure of coating, applies the mixed liquor at least one face of film base material and obtains coated film；And extension process is dried, heating, the dry coated film make it extend and form anti-charged layer.
Description
Technical field
The present invention relates to the manufacture method of the anti-charged membrane containing pi-conjugated system's electroconductive polymer.
Background technology
As the film used when packing electronic unit, widely using prevents the electrostatic of the failure cause as electronic unit
Generation anti-charged membrane.In addition, in the packaging film of food etc., food is damaged in order to prevent the attachment dust on packaging film
Deng outward appearance, sometimes using anti-charged membrane.
As anti-charged membrane, set anti-comprising surfactant at least one face of film base material for example, as it is known that having
The method of charged layer.However, in the anti-charged layer comprising surfactant, Humidity Dependence is produced in anti-charging property.
Pi-conjugated system's electroconductive polymer and polyanion are included therefore, it is proposed to be set at least one face of film base material
Anti- charged layer, the manufacture method (patent document 1~4) of the anti-charged membrane extended as needed.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-038002 publications
Patent document 2：Japanese Unexamined Patent Publication 2006-282941 publications
Patent document 3：Japanese Unexamined Patent Publication 2008-179809 publications
Patent document 4：No. 3299616 publication of Japan's patent.
The content of the invention
The invention problem to be solved
However, in the manufacture method of the anti-charged membrane described in patent document 1, there is the anti-band of the anti-charged membrane of acquirement
Electrical insufficient high situation.Moreover, in the manufacture method of the anti-charged membrane described in patent document 1, the life of anti-charged membrane
Yield is also not necessarily abundant.
In the manufacture method of the anti-charged membrane described in patent document 2, extension when pi-conjugated system's electroconductive polymer not
It can follow, it is impossible to stably manufacture anti-charged membrane.
In the manufacture method of the anti-charged membrane described in patent document 3, the sugar alcohol that anti-charged layer contains is separated out and albefaction,
Sometimes decline anti-charging property.
It is substantially, high using insulating properties to anti-charged layer in the manufacture method of the anti-charged membrane described in patent document 4
Rubber-like latex, therefore anti-charging property becomes insufficient high sometimes.
It is an object of the present invention to provide anti-charged membrane excellent in anti-charging property can stably be manufactured with high production rate
The manufacture method of anti-charged membrane.
The means to solve the problem
The present invention has following mode.
[1] manufacture method of anti-charged membrane, has：Modulating process, poly- second is mixed into electroconductive polymer aqueous dispersions
Enol, so as to modulate mixed liquor, the electroconductive polymer aqueous dispersions be containing pi-conjugated system's electroconductive polymer and it is poly- it is cloudy from
The conductive composite body of son is contained in the electroconductive polymer aqueous dispersions in water system decentralized medium；Working procedure of coating, will be described mixed
Liquid is closed to be coated at least one face of film base material and obtain coated film；And dry extension process, heating, the dry coated film
And it is extended and is formed anti-charged layer.
[2] in the manufacture method for the anti-charged membrane that [1] is recorded, further mixed to the electroconductive polymer aqueous dispersions
Heshui dispersion resin.
[3] it is poly- using amorphism as the film base material in the manufacture method of the anti-charged membrane described in [1] or [2]
Ethylene glycol terephthalate film.
[4] in the manufacture method for the anti-charged membrane that [3] are recorded, after the dry extension process, by dry painting
Applying film is heated to after more than 200 DEG C, is cooled to the crystallized temperature of the polyethylene terephthalate.
Invention effect
According to the manufacture method of the anti-charged membrane of the present invention, anti-charging property aspect can be stably manufactured with high production rate excellent
Anti- charged membrane.
Embodiment
Anti- charged membrane
Anti- charged membrane using the manufacture method manufacture of the anti-charged membrane of the present invention possesses film base material and in the film base material
The anti-charged layer that at least one face is formed.
＜ film base materials ＞
Plastic foil can be used as film base material.
As the resin material for constituting plastic foil, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene can be enumerated
It is alcohol, polyethylene terephthalate, polybutylene terephthalate (PBT), PEN, polyacrylate, poly-
Carbonic ester, Kynoar, polyarylate, styrenic elastomer, polyester elastomer, polyether sulfone, PEI, polyethers ether
Ketone, polyphenylene sulfide, polyimides, Triafol T, cellulose-acetate propionate etc..In these resin materials, from the transparency, scratch
From the point of view of in terms of property, contamination preventing and intensity, preferably polyethylene terephthalate, the more preferably poly- terephthaldehyde of amorphism
Sour glycol ester.
Plastic foil can be the film not extended, can be the film of uniaxial extension or the film of twin shaft extension.In machinery
On this aspect of excellent performance, preferably plastic foil is the film of twin shaft extension.
It is used as the average thickness for the film base material for constituting anti-charged membrane, more preferably preferably 5~400 μm, 10~200 μm.Constitute
If the average thickness of the film base material of anti-charged membrane is more than the lower limit, it is difficult to be broken, if below the higher limit,
It can ensure that as the sufficiently flexible of film.
Average thickness in this specification is to measure any 10 position thickness and the value being averaged to the measured value.
The anti-charged layer ＞ of ＜
Anti- charged layer is included：Conductive composite body containing pi-conjugated system's electroconductive polymer and polyanion, and poly- second
Enol.The anti-charged layer in manufacture method described later by dry and extend be coated onto film base material, comprising conductive composite body,
The mixed liquor of polyvinyl alcohol and water system decentralized medium and formed.
It is used as the average thickness for the anti-charged layer for constituting anti-charged membrane, more preferably preferably 10~500 μm, 20~200 μm.Structure
Average thickness into the anti-charged layer of anti-charged membrane can play fully high anti-charging property more than the lower limit, then, in institute
Anti- charged layer can be then readily formed by stating below higher limit.
(conductive composite body)
[pi-conjugated system's electroconductive polymer]
As pi-conjugated system's electroconductive polymer, if the organic polymer that main chain is made up of pi-conjugated system, as long as then having
Have the present invention effect, be just not particularly limited, can enumerate polypyrrole system electroconductive polymer, polythiophene class electroconductive polymer,
Polyacetylene (polyacetylene) class electroconductive polymer, polyphenyl class electroconductive polymer, poly- sub- phenylethylene
(polyphenylenevinylene) class electroconductive polymer, polyaniline compound electroconductive polymer, polyacene (polyacene)
Class electroconductive polymer, polythiophene sub- vinyl electroconductive polymer and its EVA etc..From the point of aerial stability
From the point of view of, preferably multi-metal polypyrrole electroconductive polymer, polythiophene class and polyaniline compound electroconductive polymer come in terms of the transparency
See, more preferably polythiophene class electroconductive polymer.
As polythiophene class electroconductive polymer, can enumerate polythiophene, poly- (3 methyl thiophene), poly- (3- ethylthiophenes),
Poly- (3- propyl group thiophene), poly- (3- butyl thiophenes), poly- (3- hexyl thiophenes), poly- (3- heptyl thiophene), poly- (3- octyl thiophenes), poly-
(3- decylthiophenes), poly- (3- dodecylthiophenes), poly- (3- octadecyls thiophene), poly- (3 bromo thiophene), poly- (3- chlorothiophenes),
Poly- (3- iodothiophens), poly- (3- cyano thiophenes), poly- (3- tolylthiophenes), poly- (3,4- thioxene), poly- (3,4- dibutyl thiophenes
Fen), poly- (3- hydroxy thiophenes), poly- (3- methoxythiophenes), poly- (3- ethoxythiophenes), poly- (3- butoxy thiophene), it is poly- (3- oneself
Epoxide thiophene), poly- (3- epoxides in heptan thiophene), poly- (3- octyloxies thiophene), poly- (3- decyloxies thiophene), poly- (3- dodecyloxies
Thiophene), poly- (3- octadecane epoxides thiophene), poly- (3,4- dihydroxy thiophene), poly- (3,4- dimethoxy-thiophene), poly- (3,4- bis-
Ethoxythiophene), poly- (3,4- dipropoxy thiophene), poly- (3,4- dibutoxy thiophene), poly- (3,4- bis- hexyloxy thiophene), poly-
(3,4- bis- heptan epoxide thiophene), poly- (3,4- bis- octyloxy thiophene), poly- (3,4- bis- decyloxy thiophene), poly- (3,4- bis- (dodecanes
Epoxide) thiophene), poly- (3,4- ethylene dioxythiophene), poly- (3,4- propylene propylenedioxythiophene), poly- (the epoxide thiophene of 3,4- butylene two
Fen), poly- (3- methyl -4- methoxythiophenes), poly- (3- methyl -4- ethoxythiophenes), poly- (3- carboxy thiophenes), it is poly- (3- methyl -
4- carboxy thiophenes), poly- (3- methyl -4- carboxy ethyls thiophene), poly- (3- methyl -4- carboxybutyls thiophene).
As multi-metal polypyrrole electroconductive polymer, can enumerate polypyrrole, poly- (N- methylpyrroles), poly- (3- methylpyrroles),
Poly- (3- N-ethyl pyrrole Ns), poly- (3- n-propyls pyrroles), poly- (3- butyl pyrroles), poly- (3- octyl groups pyrroles), poly- (3- decyls pyrroles),
Poly- (3- dodecyls pyrroles), poly- (3,4- dimethyl pyrrole), poly- (3,4- dibutyl pyrroles), poly- (3- carboxy pyrroles), poly- (3-
Methyl -4- carboxy pyrroles), poly- (3- methyl -4- carboxyethylpyrroles), poly- (3- methyl -4- carboxybutyls pyrroles), poly- (3- hydroxyls
Base pyrroles), poly- (3- methoxypyrroles), poly- (3- ethyoxyls pyrroles), poly- (3- butoxy pyrroles), poly- (3- hexyloxies pyrroles),
Poly- (3- methyl -4- hexyloxies pyrroles).
As polyaniline compound electroconductive polymer, polyaniline, poly- (2-aminotoluene), poly- (3- isobutyl-benzenes can be enumerated
Amine), poly- (2- anilinesulfonic acids), poly- (3- anilinesulfonic acids).
It is particularly preferably poly- from the point of view of electric conductivity, the transparency, the point of heat resistance in above-mentioned pi-conjugated class electroconductive polymer
(3,4- ethylene dioxythiophene).
The pi-conjugated class electroconductive polymer can be used alone one kind, two or more can also be used in combination.
[polyanion]
Polyanion be intramolecular have two or more have anion base monomer unit condensate.The polyanion
Anion base works as the dopant to pi-conjugated class electroconductive polymer, improves the conduction of pi-conjugated class electroconductive polymer
Property.
It is used as the anion base of polyanion, preferably sulfo group or carboxyl.
As the concrete example of such polyanion, polystyrolsulfon acid, polyvinyl sulfonic acid, polyallyl sulphur can be enumerated
Acid, polyacrylic acid (ester) sulfonic acid, polymethylacrylic acid (ester) sulfonic acid, poly- (2- acrylamido -2- methyl propane sulfonic acids), poly- different
Pentadiene sulfonic acid, polysulfonate ethyl (methyl) acrylate (polysulfoethylmethacrylate), poly- (4- sulphur butyl (first
Base) acrylate), the tool such as poly- methallyl epoxide benzene sulfonic acid (polymethacryloxy benzene sulfonic acid)
There is sulfonic macromolecule or with polyethylene carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic acid carboxylic acid
(polyacryl carboxylic acid), polymethylacrylic acid carboxylic acid (polymethacryl carboxylic acid),
The macromolecule of the carboxylic acid group of poly- (2- acrylamido -2- methylpropanes carboxylic acid), polyisoprene carboxylic acid, polyacrylic acid etc..Can
To be these single aggressiveness or two or more EVAs.
In these polyanions, due to anti-charging property can be improved, therefore it is preferred that with sulfonic macromolecule, more preferably gather
Styrene sulfonic acid.
The polyanion a kind of can be used alone, also can and with two or more.
The matter average molecular weight of polyanion preferably 20,000~1,000,000, more preferably 100,000~500,000.
Matter average molecular weight in this specification is to measure and set standard substance with gel permeation chromatography as polystyrene
The value obtained.
The content ratio of polyanion in conductive composite body, the preferably relatively pi-conjugated mass of system's electroconductive polymer 100
Part is the model of the scope, more preferably 10~700 mass parts, more preferably 100~500 mass parts of 1~1000 mass parts
Enclose.During the lower limit that the content ratio of polyanion is not enough, have what is died down to the doping effect of pi-conjugated system's electroconductive polymer
Trend, electric conductivity has deficiency, in addition, the water dispersible step-down of conductive composite body.On the other hand, the amount of polyanion
During more than the higher limit, the amount of pi-conjugated system's electroconductive polymer tails off, and is still difficult to obtain sufficient electric conductivity.
Polyanion forms conductive composite body by being coordinated with pi-conjugated system's electroconductive polymer.
But, in polyanion, and not all anion base is all doped in pi-conjugated system's electroconductive polymer, tool
There is remaining anion base.The remaining anion base is hydrophilic group, therefore conductive composite body has water dispersible.
(resin glue)
In anti-charged layer, in addition to conductive composite body and polyvinyl alcohol, resin glue can be also included.Binding agent
Resin is the resin beyond pi-conjugated system's electroconductive polymer, polyanion and polyvinyl alcohol, is to make pi-conjugated system's electric conductivity high score
Son and polyanion combine, improved the resin of coating strength.
In the present invention, it is used as resin glue using the resin with water dispersible.
As the concrete example of resin glue, acrylic resin, polyester resin, polyurethane resin, polyimides can be enumerated
Resin, polyether resin, melmac etc..
(alkali cpd)
Alkali cpd can be included in anti-charged layer.When including alkali cpd in anti-charged layer, the white of anti-charged layer can be suppressed
Change.
As the alkali cpd that also may be included in anti-charged layer, inorganic base, amines, quaternary ammonium salt, nitrogenous virtue can be enumerated
Fragrant race's cyclic compound etc..
As inorganic base, sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, sodium acid carbonate, saleratus, carbonic acid can be enumerated
Hydrogen ammonium etc..
As amines, aniline, toluidines, benzylamine, monoethanolamine, diethanol amine, dimethylamine, diethylamine, two can be enumerated
Propylamine, triethanolamine, trimethylamine, triethylamine, tripropyl amine (TPA) etc..
Quaternary ammonium salt, can enumerate tetramethyl ammonium, tetraethyl ammonium salt, tetrapropyl ammonium salt, tetraphenyl ammonium salt, tetrabenzyl ammonium salt,
Four naphthyl ammonium salts, 1- ethyl-3-methylimidazole hydroxide etc..
As nitrogenous aromatic series cyclic compound, imidazoles, 2-methylimidazole, 2- propyl imidazoles, 1- (2- hydroxyls can be enumerated
Ethyl) imidazoles, 2-ethyl-4-methylimidazole, DMIZ 1,2 dimethylimidazole, 1- cyano ethyls -2-methylimidazole, 1- cyano ethyls -
2-ethyl-4-methylimidazole, 2- aminobenzimidazoles, pyridine etc..
Above-mentioned alkali cpd can be used alone one kind, also can and with two or more.
(hydroxy-containing compounds)
The hydroxy-containing compounds with more than three hydroxyls can be included in anti-charged layer.Contain hydroxyl comprising described in anti-charged layer
During based compound, anti-charging property can be further improved.When in anti-charged layer containing hydroxy-containing compounds of the hydroxyl value less than three,
The effect for improving anti-charging property can not fully be obtained.
As hydroxy-containing compounds, the aromatic series for the hydroxyl that more than three are combined in alcoholic compounds, aromatic rings can be enumerated
Class hydroxy-containing compounds etc..The hydroxy-containing compounds are not condensates.
As alcoholic compounds, D-sorbite (95 DEG C of fusing point), xylitol (92~96 DEG C of fusing point), maltitol can be enumerated
(145 DEG C of fusing point), erythrite (121 DEG C of fusing point), mannitol (166~168 DEG C of fusing point), inositol (225~227 DEG C of fusing point),
Lactitol (150 DEG C of fusing point) etc..
As fragrant same clan's hydroxy-containing compounds, pyrogallol (131~134 DEG C of melting point), gallic acid (melting point can be enumerated
250 DEG C), propylgallate (150 DEG C of melting point) etc..
The hydroxy-containing compounds can be used alone one kind, also can and with two or more.
The preferred melting point of hydroxy-containing compounds is less than 150 DEG C compounds, and more preferably less than 135 DEG C of compound enters one
Step is preferably less than 100 DEG C of compound.When the melting point of hydroxy-containing compounds is below the higher limit, the anti-band of anti-charged layer
Electrically further uprise.On the other hand, the melting point of hydroxy-containing compounds is preferably more than 50 DEG C.
In addition, the melting point of hydroxy-containing compounds can be obtained with differential thermal analysis (DSC).
(additive)
Known additive can be included in anti-charged layer.
As additive, as long as the effect with the present invention, there is no particular restriction, for example, can use surfactant, nothing
Machine conductive agent, defoamer, coupling agent, antioxidant, ultra-violet absorber etc..But, additive is by the polyanion, described
Compound group beyond alkali cpd and the hydroxy-containing compounds into.
As surfactant, nonionic class, anionic species, cationic surfactant can be enumerated, but it is stable from preserving
From the point of view of in terms of property, preferred nonionic class.In addition, can also add the polymerization species table such as polyvinyl alcohol, PVP
Face activating agent.
As inorganic conductive agent, metal ion class, conductive carbon etc. can be enumerated.In addition, metal ion can be by making metal
Salt is dissolved in water to generate.
As defoamer, silicone resin, dimethyl silicone polymer, organic siliconresin etc. can be enumerated.
As coupling agent, vinyl, amino, silane coupler with epoxy radicals etc. can be enumerated.
As antioxidant, phenol antioxidant, amine antioxidants, phosphorous antioxidant, sulphur class can be enumerated anti-oxidant
Agent, carbohydrate, vitamins etc..
As ultra-violet absorber, can enumerate Benzotriazole Ultraviolet Stabilizer, benzophenone ultraviolet absorbent,
Salicylate ultraviolet absorbent, cyanoacrylate ultraviolet absorbent, oxanilide (oxanilide) class are ultraviolet
Light absorbers, hindered amines ultra-violet absorber, benzoic ether (benzoate) class ultra-violet absorber etc..
The manufacture method of anti-charged membrane
The manufacture method of the anti-charged membrane of the present invention has modulating process, working procedure of coating and dries extension process.
＜ modulating process ＞
Modulating process is set to electroconductive polymer aqueous dispersions mixing pva and according to it is expected that mixing water is dispersed
Fat and the process for modulating mixed liquor.
Here, electroconductive polymer aqueous dispersions are the electric conductivity containing pi-conjugated system's electroconductive polymer and polyanion
Complex is contained in the dispersion liquid in water system decentralized medium.
In modulating process, in order to improve the anti-charging property of anti-charged membrane, it can add into electroconductive polymer aqueous dispersions
Plus stating hydroxy-containing compounds.In addition, in modulating process, can be to electroconductive polymer in order to suppress the albefaction of anti-charged layer
Above-mentioned alkali cpd is added in aqueous dispersions.Moreover, above-mentioned additive can be added into electroconductive polymer aqueous dispersions.
When adding alkali cpd, the pH (25 DEG C) for preferably adding the mixed liquor is changed into 3~10 amount, more preferably adds
5~9 amount.The pH of the mixed liquor can improve the anti-charging property of anti-charged layer in the scope, then, further suppress white
Change.
(water system decentralized medium)
Water system decentralized medium is the mixture of water or water and water-miscible organic solvent.Water in water system decentralized medium contains
Ratio is preferably more than 50 mass % more preferably more than 80 mass %.On the other hand, the content ratio of water system decentralized medium reclaimed water
Preferably below 95 mass %.That is, the content ratio of water system decentralized medium reclaimed water preferably 50~95 mass %, more preferably 80~95
Quality %.
As water-miscible organic solvent, the solvent that solubility parameter is more than 10 can be enumerated, for example, monoalcohol solvent, containing
Nitrogen-atoms polar solvent, phenolic solvent, multivalence aliphatic alcohol solvent, carbonate solvent, ether solvents, heterocyclic compound, nitrilation are closed
Thing etc..
As monoalcohol solvent, methanol, ethanol, isopropanol etc. can be enumerated.
As nitrogen atom polar solvent, METHYLPYRROLIDONE, N- methylacetamides, N, N- dimethyl can be enumerated
Formamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, hexa-methylene phosphoric triamide, NVP, N- vinyl first
Acid amides, N- vinyl acetamides etc..Nitrile compound is not included in nitrogen atom polar solvent.
As phenol solvent, cresols, phenol, xylenols etc. can be enumerated.
As multivalence aliphatic alcohol solvent, ethylene glycol, propane diols, DPG, 1,3-BDO, isoamyl two can be enumerated
Alcohol, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, 1,9- nonanediols, neopentyl glycol etc..
As carbonate solvent, ethylene carbonate, propylene carbonate etc. can be enumerated.
As ether solvents, dioxane, diethyl ether, propane diols dialkyl ether, dialkylethers, poly- the third two can be enumerated
Alcohol dialkyl ether etc..
As heterocyclic compound, 3- methyl -2- oxazolidones etc. can be enumerated.
In nitrile compound, acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile etc. can be enumerated.
These solvents can be used alone one kind, can also be used as two or more mixtures.Wherein, from the viewpoint of stability
From the point of view of, at least one preferably selected from the group being made up of methanol, ethanol, isopropanol and dimethyl sulfoxide.
(polyvinyl alcohol)
Polyvinyl alcohol works as the dispersant of conductive composite body and water-dispersed resin.By making to wrap in mixed liquor
Containing polyvinyl alcohol, when extending coated film in drying extension process, extensibility is uprised.
Polyvinyl alcohol is manufactured by the acetyl group of saponified polyvinyl acetate, but the acetyl group of some is not yet sometimes
Saponification.Therefore, polyvinyl alcohol is sometimes with vinylacetate unit.The saponification degree of the polyvinyl alcohol used in the present invention is preferred
For 70~100%.The saponification degree of polyvinyl alcohol is that more than the lower limit, then can simply be dissolved in the water.
The matter average molecular weight of polyvinyl alcohol is preferably 1000~100000, and more preferably 1300~60000.Polyvinyl alcohol
Matter average molecular weight then can fully improve the extensibility of coated film described later more than the lower limit, the higher limit with
If lower, the dissolubility to water can be improved.
(water-dispersed resin)
Water-dispersed resin is the resin being dispersed in electroconductive polymer aqueous dispersions, in anti-charged layer, is viscous
Tie agent resin.
As the concrete example of water-dispersed resin, acrylic resin, polyester resin, polyurethane resin, polyamides can be enumerated sub-
Polyimide resin, melmac etc. have the acidic group of carboxyl or sulfo group etc. or the hydrophilic resin of its salt.
As other concrete examples of water-dispersed resin, acrylic resin can be enumerated, polyester resin, polyurethane resin, poly-
The lo-tionized resin such as imide resin, melmac.
In above-mentioned resin, due to can further improve anti-charging property, as water-dispersed resin, preferably with acidic group or its
The polyester resin of salt, the polyurethane resin with acidic group or its salt, the polyester resin of emulsion form, the polyurethane resin of emulsion form.
The water-dispersed resin can be used alone one kind, also can and with two or more.
From the point of view of the point of the physical property of anti-charged layer, preferably the glass transition temperature of water-dispersed resin is more than 0 DEG C.This
Outside, glass transition temperature can measure (DSC) with Differential Scanning Calorimeter and obtain.
The polyether resin of polyethylene glycol or polyalkylene oxide etc. is the resin with water dispersible, but brings albefaction sometimes and anti-
The decline of charging property, it is not preferable.
It is thus impossible to which using polyether resin as water-dispersed resin, polyether resin is not preferably included in anti-charged layer.
(content ratio)
The mass % of gross mass 100 of the content ratio preferred pair mixed liquor of polyvinyl alcohol in mixed liquor is 0.01~10 matter
Measure %, more preferably 0.1~5 mass %.The content ratio of polyvinyl alcohol can then improve coated film more than the lower limit
Extensibility, below the higher limit, then can suppress the decline of anti-charging property.
The content ratio of water system decentralized medium in mixed liquor with respect to mixed liquor gross mass 100 mass %, preferably 50
~90 mass %, more preferably 70~90 mass %.The content ratio of water system decentralized medium is more than the lower limit, then easily
Disperse each composition, screening characteristics can be improved, below the higher limit, then solid component concentration is high, in primary coating easily really
Protect thickness.
Water dispersible tree is being included in mixed liquor to electroconductive polymer aqueous dispersions addition above-mentioned water-dispersed resin
During fat, the mass parts of solid constituent 100 of the content ratio facing conductive sex camplex of the water-dispersed resin in mixed liquor, preferably
For 100~10000 mass parts, more preferably more preferably 100~5000 mass parts, 100~1000 mass parts.Moisture dissipates
The content ratio of property resin can then improve Film making properties and film-strength more than the lower limit.However, water-dispersed resin contains
Proportional when exceeding the higher limit, the content ratio of conductive composite body declines, and anti-charging property declines sometimes.
Above-mentioned hydroxy-containing compounds are being added to electroconductive polymer aqueous dispersions and mixed liquor includes hydroxy-containing compounds
When, the content ratio of the hydroxy-containing compounds in mixed liquor, the mass parts of solid constituent 100 of facing conductive sex camplex are preferably
10~1000 mass parts, more preferably 10~500 mass parts, more preferably 10~200 mass parts.Hydroxy-containing compounds
Content ratio then can further improve anti-charging property more than the lower limit.However, the content ratio of hydroxy-containing compounds surpasses
When crossing the higher limit, the content ratio relative drop of conductive composite body, anti-charging property declines on the contrary sometimes.
When including additive to the above-mentioned additive of electroconductive polymer aqueous dispersions addition and mixed liquor, in mixed liquor
The content ratio of additive suitably determines according to the species of additive, the matter of solid constituent 100 of usual facing conductive sex camplex
Part is measured, in the range of 0.001~5 mass parts.
(enhancement of dispersion processing)
To electroconductive polymer aqueous dispersions, it can implement to assign shear strength and improve the electric conductivity in water system decentralized medium to answer
Fit dispersed enhancement of dispersion processing.
In enhancement of dispersion processing, dispersion machine is preferably used.As dispersion machine, homogenizer, high pressure homogenizer, pearl can be enumerated
Grinding machine etc., wherein it is preferred that high pressure homogenizer.
High pressure homogenizer is, for example, to possess to having carried out the pressurizations such as the electroconductive polymer aqueous dispersions of enhancement of dispersion processing
High pressure generating unit and the opposite impact portions or hole portion or slit portion disperseed.As high pressure generating unit, suitably use
The high-pressure pump of plunger pump etc..
High-pressure pump has the various forms of single-plicate, twin, tri-coupling type etc., but the present invention can use any form.
As the specific example of high pressure homogenizer, can enumerate the industrial company system of Jitian's machinery trade name Nanomizer,
Microfluidisc Altimizer of trade name Microfluidizer, Shan Ye Mechanology Inc. etc..
(mixing of polyvinyl alcohol and water-dispersed resin)
In the mixing of polyvinyl alcohol, poly- second is mixed in the electroconductive polymer aqueous dispersions preferably handled to enhancement of dispersion
Enol and obtain mixed liquor.In the mixing of polyvinyl alcohol, the electroconductive polymer aqueous dispersions preferably handled to enhancement of dispersion
It is stirred after the central or addition of middle addition polyvinyl alcohol.
In mixing water dispersion resin, preferably into the electroconductive polymer aqueous dispersions for having carried out enhancement of dispersion processing
Mixing water dispersion resin and obtain mixed liquor.When carrying out the mixing of water-dispersed resin, preferably handled to enhancement of dispersion
Electroconductive polymer aqueous dispersions addition water-dispersed resin in or addition after be stirred.
Water-dispersed resin can be mixed into electroconductive polymer aqueous dispersions with the state of solid content, it is also possible to water-soluble
The mode of liquid or aqueous dispersions (slurries or emulsion) is mixed into electroconductive polymer aqueous dispersions.
＜ working procedure of coating ＞
Working procedure of coating is the process that the mixed liquor is coated at least one face of film base material and coated film is obtained.
Apply the film base material of mixed liquor, i.e., as the average thickness before extension, preferably 10~500 μm, more preferably 20~
200μm.It is difficult to be broken if the average thickness of film base material is more than the lower limit, below the higher limit, then can ensure that
It is flexible as the abundance of film.
As the method for coating mixed liquor, it can be applicable for example using gravure coater, roll coater, curtain coater, spin coating
Machine, rod coater (bar coater), reverse coating machine, kiss apply machine, fountain type coating machine, screw mandrel coating machine (rod
Coater), Kohler coater, knife coating machine (knife coater), knife type coater (blade), cast coat machine, curtain formula are applied
The coating method of the coating machine of machine etc., uses the spray method of the sprayer of aerial spraying, airless spraying, rotor damping etc., leaching
Dipping method of stain etc. etc..
In the above method, for can easily apply, sometimes using rod coater.In rod coater, applied thickness with
Species and it is different, in commercially available rod coater, by species additional numbers, its numbering is bigger, then can apply thicker.
There is no particular restriction for coating amount of the mixed liquor to base material, but is used as solid constituent, preferably 0.1~2.0g/m2
Scope.
＜ dries extension process ＞
It is that the heating coated film makes the process that it is dried and extended to dry extension process.The mixed liquor of coating is set to dry simultaneously
Extension, can form anti-charged layer.In addition, by extending coated film, the anti-powered of large area can also be obtained by reducing surface covered
Film, can improve the productivity ratio of anti-charged membrane.
The heating-up temperature for drying the coated film in extension process is preferably more than the boiling point of water system decentralized medium.In addition, applying
The heating-up temperature of applying film is preferably less than 200 DEG C, more preferably less than 180 DEG C.That is, the heating-up temperature of coated film is preferably water system point
More than the boiling point of dispersion media less than 200 DEG C, more preferably more than the boiling point of water system decentralized medium less than 180 DEG C.
As the heating means of coated film, the usual method such as can use Hot-blast Heating or infrared heating.
In extension process is dried, at least a portion of polyvinyl alcohol is decomposed and disappeared sometimes, but is dissipated without using moisture
During property resin, heating-up temperature is preferably adjusted so that the decomposition of polyvinyl alcohol is inhibited.Specifically, heating-up temperature is preferably set
For more than the boiling point of water system decentralized medium less than 150 DEG C.
The average thickness of the film before extension after the dried coating film of mixed liquor, preferably 20~1000 μm, more preferably 40
~400 μm.The average thickness of the film before extension after the dried coating film of mixed liquor can be played fully more than the lower limit, then
High anti-charging property, can then be readily formed anti-charged layer below the higher limit.
In extension process is dried, coated film can be made to be extended while drying, can also be extended after the drying.With doing
It is dry to extend simultaneously, or extend after the drying, then it can utilize to dry and assign the heat of coated film to soften film base material.Therefore,
The efficiency of the energy for obtaining anti-charged membrane can be improved.
When using uniaxial extension film as film base material, preferably extend to the direction vertical with the direction of extension.For example,
During using the uniaxial extension film extended along its length as film base material, preferably extend in the width direction.
The extension ratio of preferred coated film is 2~5 times.If extension ratio is more than the lower limit, can further it carry
The productivity ratio of high anti-charged membrane, can then prevent the rupture of film below the higher limit.
＜ crystallization steps ＞
, also can be after extension process be dried as film base material when using amorphism polyethylene terephthalate film
With crystallization step.
In crystallization step, after dry coated film is heated into its surface temperature more than 200 DEG C, carry out cold
But, untill the crystallized temperature of not enough polyethylene terephthalate.
When surface temperature is heated into more than 200 DEG C, the amorphism polyethylene terephthalate of film base material is constituted
At least a portion starts to melt.After it melts, the crystallization of not enough polyethylene terephthalate is cooled in surface temperature
During temperature, the amorphism polyethylene terephthalate of a part for melting is crystallized and solidified simultaneously.Thus, film base can be made
Material is changed into crystallinity polyethylene terephthalate film.The film base material being made up of crystallinity polyethylene terephthalate film
It is excellent in the mechanical properties of tensile strength etc..
＜ action effects ＞
It is anti-powered using pi-conjugated system's electroconductive polymer as contributing in the manufacture method of above-mentioned anti-charged membrane
Conductive component, therefore anti-charging property is difficult to be influenceed by humidity etc..
In addition, in above-mentioned manufacture method, contain polyvinyl alcohol by making to be coated in the mixed liquor of film base material, can be fully
Improve the anti-charging property of obtained anti-charged membrane.Moreover, by making the mixed liquor for being coated to film base material contain polyvinyl alcohol, can carry
The extensibility of high coated film.Therefore, in above-mentioned manufacture method, area can easily be manufactured than surface covered greatly anti-powered
Film, it is excellent in terms of productivity ratio, it is also excellent in terms of the stability of production.
In addition, in the manufacture method of the anti-charged membrane with above-mentioned process, making film base material using extrusion molding, making
Mixed liquor described in continuously coating while the film base material of the making advances, can be thermally dried and prolong after the continuously coating
Stretch.Or, in the manufacture method of the anti-charged membrane with above-mentioned process, film base material is released successively from the film base material of roll,
The film base material released successively is advanced and mixed liquor described in continuously coating, can be thermally dried simultaneously after the continuously coating
Extension.That is, in above-mentioned manufacture method, anti-charged membrane can be continuously manufactured by from film base material.In continuous manufacture, can further it carry
The productivity ratio of high anti-charged membrane.
(preferred embodiment)
(a) preferred embodiment of the manufacture method of anti-charged membrane of the invention has：Modulating process, to electroconductive polymer water
Mixing pva and mixed liquor is modulated in dispersion liquid, electroconductive polymer aqueous dispersions are containing polythiophene class electric conductivity high score
The electroconductive polymer moisture that the conductive composite body of polyanion and with sulfo group is contained in water system decentralized medium dissipates
Liquid；Working procedure of coating, the mixed liquor is applied at least one face of film base material and coated film is obtained；And dry extension process,
Heating, the dry coated film make it extend and form anti-charged layer.
(b) the more preferably mode of the manufacture method of anti-charged membrane of the invention has：Modulating process, to electroconductive polymer
Mixing pva and water-dispersed resin in aqueous dispersions, so as to modulate mixed liquor, electroconductive polymer aqueous dispersions are to contain
The conductive composite body for having polythiophene class electroconductive polymer and the polyanion with sulfo group is contained in water system decentralized medium
Electroconductive polymer aqueous dispersions；Working procedure of coating, applies the mixed liquor at least one face of film base material and is applied
Film；And extension process is dried, heating, the dry coated film make it extend and form anti-charged layer, wherein, the moisture dissipates
Property resin be selected in the group being made up of polyester, polyurethane, polyester-polyurethane more than one.
(c) further preferred embodiment of the manufacture method of anti-charged membrane of the invention has：Modulating process is high to electric conductivity
Mixing pva, water-dispersible polyester and alkali cpd in molecule aqueous dispersions, thus modulate pH at 25 DEG C for 5~
9 mixed liquor, electroconductive polymer aqueous dispersions are the conductions containing poly- (3,4-rthylene dioxythiophene) and polystyrolsulfon acid
Sex camplex is contained in the electroconductive polymer aqueous dispersions in water；Working procedure of coating, institute is applied at least one face of film base material
State mixed liquor and obtain coated film；And extension process is dried, the coated film is heated into 100~180 DEG C makes it dry simultaneously
Extend 2~5 times and form anti-charged layer.
[embodiment]
The modulation of (modulation example 1) polystyrolsulfon acid
206g SSS is dissolved into 1000ml ion exchange water, is stirred and in 20 minute phase at 80 DEG C
Between drip the water for being previously dissolved in 10ml 1.14g ammonium persulfate oxidizing agent solution, stir the solution 12 hours.
10 mass % sulfuric acid is diluted to the obtained addition of the solution containing SSS 1000ml, ultrafiltration is used
The about 1000ml solution of the solution containing polystyrolsulfon acid is removed, 2000ml ion exchange water is added into raffinate, using super
Filter method removes about 2000ml solution.Above-mentioned ultrafiltration in triplicate.
Then, about 2000ml ion exchange water is added into obtained filtrate, it is molten to remove about 2000ml using ultrafiltration
Liquid.The ultrafiltration in triplicate.
The water in obtained solution is removed under reduced pressure, the solid content of colourless polystyrolsulfon acid is obtained.
The modulation of the aqueous dispersions of (modulation example 2) poly- (3,4- ethene dioxythiophenes)-polystyrolsulfon acid (PEDOT-PSS)
14.2g 3,4- ethene dioxythiophenes are mixed at 20 DEG C and 36.7g polystyrolsulfon acid is dissolved in
The solution of 2000ml ion exchange water.
Thus obtained mixed solution is maintained at 20 DEG C and mixed, the ion exchange water that is dissolved in 200ml is slowly added
The oxidation catalysis solution of 29.64g ammonium persulfate and 8.0g ferrous sulfate, stirring brings it about reaction in 3 hours.
2000ml ion exchange water is added to obtained reaction solution, about 2000ml solution is removed using ultrafiltration.Repeat
The operation three times.
Then, the 200ml sulfuric acid for being diluted to 10 mass % and 2000ml ion exchange water are added to obtained solution,
About 2000ml solution is removed using ultrafiltration, 2000ml ion exchange water is added to, is removed about using ultrafiltration
2000ml liquid.Repeat the operation three times.
And then, 2000ml ion exchange water is added to obtained solution, about 2000ml solution is removed using ultrafiltration.
The operation five times is repeated, about 1.2 mass % blue PEDOT-PSS aqueous dispersions are obtained.
(Production Example 1)
After above-mentioned PEDOT-PSS aqueous dispersions 30g, water 60g and imidazoles 0.135g is mixed, high pressure dispersing machine is used
The pressure that (the industrial company system Nanomizer of Jitian's machinery) assigns 100MPa carries out enhancement of dispersion processing.To utilizing enhancement of dispersion
Handle obtain the first mixed liquor addition water-dispersible polyester (mutual induction chemical industrial company system, PlasCoatRZ-105, solid into
Point mass % of concentration 25) 10g and polyvinyl alcohol (Kuraray company systems, Kuraray PovalPVA210, saponification degree 88%, matter
Average molecular weight 50000) 0.5g, obtain the second mixed liquor.
Second mixed liquor is coated to amorphism polyethylene terephthalate film (A- using No.4 rod coater
PET film, 72 DEG C of glass transition temperature) on.Using film twin shaft extension apparatus (the made IMC-11A9 of this making of well) in 130 DEG C of temperature
Degree is lower to heat and dries the coated film obtained by the coating, and 2 times are extended along the width of film.Thus, obtain having and prevent powered
The anti-charged membrane of layer.
(Production Example 2)
In addition to the extension ratio of the width of film is 4 times, anti-charged membrane is obtained in the same manner as Production Example 1.
(Production Example 3)
Except water-dispersible polyester (PlasCoatRZ-105) is changed into water-dispersible polyester (mutual induction chemical industrial company
System, PlasCoatZ-880, the mass % of solid component concentration 25) beyond, anti-charged membrane is obtained in the same manner as Production Example 1.
(Production Example 4)
Except water-dispersible polyester (PlasCoatRZ-105) is changed into water-dispersible polyester (mutual induction chemical industrial company
System, PlasCoatZ-565, the mass % of solid component concentration 25) beyond, anti-charged membrane is obtained in the same manner as Production Example 1.
(Production Example 5)
Except water-dispersible polyester (PlasCoatRZ-105) is changed into water-dispersible polyester (mutual induction chemical industrial company
System, PlasCoatZ-690, the mass % of solid component concentration 25) beyond, anti-charged membrane is obtained in the same manner as Production Example 1.
(Production Example 6)
Except water-dispersible polyester (PlasCoatRZ-105) is changed into water-dispersible polyester (mutual induction chemical industrial company
System, PlasCoatZ-3310, the mass % of solid component concentration 25) beyond, anti-charged membrane is obtained in the same manner as Production Example 1.
(Production Example 7)
Except water-dispersible polyester (PlasCoatRZ-105) is changed into water-dispersible polyester (mutual induction chemical industrial company
System, PlasCoatZ-570, the mass % of solid component concentration 25) beyond, anti-charged membrane is obtained in the same manner as Production Example 1.
(Production Example 8)
Except by the quantitative change of polyvinyl alcohol (Kuraray company systems, Kuraray Poval PVA210) be 0.25g beyond,
Anti- charged membrane is obtained in the same manner as Production Example 3.
(Production Example 9)
Except by the quantitative change of polyvinyl alcohol (Kuraray company systems, Kuraray Poval PVA210) be 1.0g beyond, with
Production Example 3 similarly obtains anti-charged membrane.
(Production Example 10)
Except polyvinyl alcohol (Kuraray company systems, Kuraray Poval PVA210) is changed into polyvinyl alcohol, (Japan closes
Into chemical company's system, Gohsenol GM14L, saponification degree 86.5~89.0%, matter average molecular weight 1500) beyond, with Production Example 3
Similarly obtain anti-charged membrane.
(Production Example 11)
It is 80g by the quantitative change of water, the quantitative change of imidazoles is 0.045g except being 10g by the quantitative change of PEDOT-PSS aqueous dispersions
In addition, anti-charged membrane is obtained in the same manner as Production Example 3.
(Production Example 12)
After the anti-charged membrane obtained in Production Example 3 is again heated into 240 DEG C, temperature is slowly dropped to 130 DEG C, make
Amorphism polyethylene terephthalate is crystallized, and A-PET films is turned into crystallinity PET film.
(Production Example 13)
Except water-dispersible polyester (mutual induction chemical industrial company system, PlasCoatRZ-105) is changed into polyurethane, (DIC is public
Department's system, BONDIC 2210, the mass % of solid component concentration 40) beyond, anti-charged membrane is obtained in the same manner as Production Example 1.
(Production Example 14)
Except water-dispersible polyester (mutual induction chemical industrial company system, PlasCoatRZ-105) is changed into BONDIC 2220
Beyond (DIC company systems, polyester fiber-polyurethane, the mass % of solid component concentration 40), anti-band is obtained in the same manner as Production Example 1
Electrolemma.
(Production Example 15)
Except water-dispersible polyester (mutual induction chemical industrial company system, PlasCoatRZ-105) is changed into BONDIC 2260
Beyond (DIC company systems, polyurethane, the mass % of solid component concentration 40), anti-charged membrane is obtained in the same manner as Production Example 1.
(Production Example 16)
Except water-dispersible polyester (mutual induction chemical industrial company system, PlasCoatRZ-105) is changed into water-dispersible polyester
(mutual induction chemical industrial company system, PlasCoatZ-565, solid component concentration 25%), Kuraray Poval PVA210 are become
Beyond Kuraray Poval LM25 (saponification degree 33.0~38.0, matter average molecular weight 18000), in the same manner as Production Example 1
To anti-charged membrane.
(Production Example 17)
Except water-dispersible polyester (mutual induction chemical industrial company system, PlasCoatRZ-105) is changed into water-dispersible polyester
(mutual induction chemical industrial company system, PlasCoatZ-880, the mass % of solid component concentration 25), by Kuraray Poval
PVA210 is changed into beyond Kuraray Poval LM25 (saponification degree 33.0~38.0, weight-average molecular weight 18000), with manufacture
Example 1 similarly obtains anti-charged membrane.
(Production Example 18)
After above-mentioned PEDOT-PSS aqueous dispersions 30g, water 70g and imidazoles 0.135g is mixed, high pressure dispersing machine is used
The pressure that (the industrial company system Nanomizer of Jitian's machinery) assigns 100MPa carries out enhancement of dispersion processing.To utilizing enhancement of dispersion
Obtained the first mixed liquor addition polyvinyl alcohol (Kuraray company systems, Kuraray Poval PVA210) 0.5g is handled, is obtained
Second mixed liquor.
Second mixed liquor is coated to amorphism polyethylene terephthalate film (A- using No.4 rod coater
PET film, 72 DEG C of glass transition temperature) on.Using film twin shaft extension apparatus (the made IMC-11A9 of this making of well) in 130 DEG C of temperature
Degree is lower to heat and dries the coated film obtained by the coating, and 2 times are extended along the width of film.Thus, obtain having and prevent powered
The anti-charged membrane of layer.
(Production Example 19)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 1.
(Production Example 20)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 2.
(Production Example 21)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 3.
(Production Example 22)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 4.
(Production Example 23)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 5.
(Production Example 24)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 6.
(Production Example 25)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 7.
(Production Example 26)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 8.
(Production Example 27)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 9.
(Production Example 28)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 10.
(Production Example 29)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 11.
(Production Example 30)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 13.
(Production Example 31)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 14.
(Production Example 32)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 15.
(Production Example 33)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 16.
(Production Example 34)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 17.
(Production Example 35)
In addition to without polyvinyl alcohol, film is obtained in the same manner as Production Example 18.
(Production Example 36)
Mix after PEDOT-PSS aqueous dispersions 30g, water 60g and imidazoles 0.135g, use high pressure dispersing machine (Jitian's machinery
Industrial company system Nanomizer) assign 100MPa pressure carry out enhancement of dispersion processing.Water dispersible is added to obtained liquid
Polyester (mutual induction chemical industrial company system, PlasCoatZ-880, the mass % of solid component concentration 25) 10g and polyethylene glycol are (average
Molecular weight 1000) 0.3g, obtain mixed liquor.
Obtained mixed liquor is coated to amorphism polyethylene terephthalate film (A- using No.4 rod coater
PET film, 72 DEG C of glass transition temperature) on.Using film twin shaft extension apparatus (the made IMC-11A9 of this making of well) in 130 DEG C of temperature
Degree is lower to heat and dries the coated film obtained by the coating, and 2 times are extended along the width of film.Thus, obtain having and prevent powered
The anti-charged membrane of layer.
＜ evaluates ＞
The sheet resistance value of each anti-charged membrane is measured using resistrivity meter (Mitsubishi Chemical's resistrivity meter).Table 1,2 is shown
Measurement result.Sheet resistance value is smaller, then anti-charging property is better.In addition, " OVER " means more than measurable range in table
The upper limit.
Table 1
Table 2
It is coated to by the mixed liquor for also including polyvinyl alcohol in addition to PEDOT-PSS in the Production Example 1~18 of film base material,
The sheet resistance value of anti-charged membrane is fully small, and anti-charging property is especially excellent.
Mixed liquor comprising PEDOT-PSS but not comprising polyvinyl alcohol is being coated to the Production Example 19~35 of film base material
In, the anti-charging property step-down of obtained anti-charged membrane.In Production Example 19~35, anti-charging property is low, it is believed that because mixed
Close liquid and do not include polyvinyl alcohol, extensibility becomes insufficient, defect is produced in anti-charged layer.
It will be coated in the Production Example 36 of film base material, obtaining to substitute the mixed liquor of polyvinyl alcohol comprising polyethylene glycol
The anti-charging property of anti-charged membrane is also low.
Utilization possibility in industry
The anti-charged membrane obtained in the present invention can be suitably used for electronic parts film, food packaging film etc..
Claims (3)
1. a kind of manufacture method of anti-charged membrane, has：
Modulating process, by polyvinyl alcohol by the content ratio of the polyvinyl alcohol in the way of the mass % of 0.01 mass %~10 to
Mixed in electroconductive polymer aqueous dispersions, so as to modulate mixed liquor, the electroconductive polymer aqueous dispersions are containing pi-conjugated
It is that the conductive composite body of electroconductive polymer and polyanion is contained in the electroconductive polymer moisture in water system decentralized medium
Dispersion liquid,
Working procedure of coating, applies the mixed liquor at least one face of film base material, obtains coated film, and
Extension process is dried, heating, the dry coated film simultaneously extend it, so that anti-charged layer is formed,
The film base material is used as using amorphism polyethylene terephthalate film.
2. the manufacture method of anti-charged membrane according to claim 1, wherein,
Mixing water dispersion resin is gone back into the electroconductive polymer aqueous dispersions.
3. the manufacture method of anti-charged membrane according to claim 1, wherein,
After the dry extension process, after dry coated film is heated to more than 200 DEG C, it is cooled to described poly- to benzene two
The crystallized temperature of formic acid second diester.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-173203 | 2014-08-27 | ||
| JP2014173203A JP5872004B1 (en) | 2014-08-27 | 2014-08-27 | Method for producing antistatic film |
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| CN105385313A CN105385313A (en) | 2016-03-09 |
| CN105385313B true CN105385313B (en) | 2017-09-15 |
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| US (1) | US9546310B2 (en) |
| EP (1) | EP2995643B1 (en) |
| JP (1) | JP5872004B1 (en) |
| KR (1) | KR101670252B1 (en) |
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| JP6520559B2 (en) * | 2015-08-20 | 2019-05-29 | 三菱ケミカル株式会社 | Conductive composition, conductor, and laminate comprising the conductor |
| JP2017039851A (en) * | 2015-08-20 | 2017-02-23 | 三菱レイヨン株式会社 | Conductive composition, conductor and laminate having the conductor formed therein |
| JP6849271B2 (en) * | 2016-04-28 | 2021-03-24 | 昭和電工株式会社 | Method for manufacturing conductive film |
| JP2017215367A (en) * | 2016-05-30 | 2017-12-07 | ナガセケムテックス株式会社 | Laminate for polarization films and method for producing the same |
| JP6745153B2 (en) * | 2016-07-11 | 2020-08-26 | 信越ポリマー株式会社 | Paint for forming conductive release layer and method for producing the same, and conductive release film and method for producing the same |
| JP6640046B2 (en) * | 2016-07-11 | 2020-02-05 | 信越ポリマー株式会社 | Manufacturing method of antistatic film |
| JP6960310B2 (en) * | 2016-12-07 | 2021-11-05 | ナガセケムテックス株式会社 | Rough surface conductors and biological sensing devices |
| JP6845002B2 (en) * | 2016-12-13 | 2021-03-17 | 信越ポリマー株式会社 | Manufacturing method of antistatic film |
| JP6832724B2 (en) * | 2017-01-30 | 2021-02-24 | 信越ポリマー株式会社 | Manufacturing method of antistatic film |
| JP6832749B2 (en) * | 2017-03-06 | 2021-02-24 | 信越ポリマー株式会社 | Manufacturing method of antistatic film |
| JP6932627B2 (en) * | 2017-12-06 | 2021-09-08 | 信越ポリマー株式会社 | Method for manufacturing conductive polymer dispersion liquid and method for manufacturing conductive film |
| JP7269810B2 (en) * | 2019-07-11 | 2023-05-09 | 信越ポリマー株式会社 | Conductive polymer dispersion, conductive film and method for producing same |
| TWI819397B (en) * | 2020-10-26 | 2023-10-21 | 日商信越聚合物股份有限公司 | Conductive polymer dispersion and its manufacturing method, conductive polymer-containing liquid and its manufacturing method, conductive laminate and its manufacturing method, and capacitor and its manufacturing method |
| WO2023176543A1 (en) * | 2022-03-15 | 2023-09-21 | 東レ株式会社 | Laminated polyester film |
| CN117624982B (en) * | 2023-11-08 | 2024-05-28 | 苏州市星辰新材料集团有限公司 | Water-based antistatic coating material and preparation method thereof |
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| KR101670252B1 (en) | 2016-10-28 |
| US9546310B2 (en) | 2017-01-17 |
| CN105385313A (en) | 2016-03-09 |
| US20160060497A1 (en) | 2016-03-03 |
| TW201607977A (en) | 2016-03-01 |
| EP2995643A1 (en) | 2016-03-16 |
| TWI554558B (en) | 2016-10-21 |
| JP5872004B1 (en) | 2016-03-01 |
| EP2995643B1 (en) | 2017-03-22 |
| JP2016047501A (en) | 2016-04-07 |
| KR20160025458A (en) | 2016-03-08 |
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